removal of heavy metals from aqueous ...iwtc.info/wp-content/uploads/2017/05/31.pdf2017/05/31 ·...

Twentieth International Water Technology Conference, IWTC20Hurghada, 18-20 May 2017

177

REMOVAL OF HEAVY METALS FROM AQUEOUS SOLUTIONS BY

ADSORPTION ONTO MODIFIED CELLULOSE: EQUILIBRIUM,

KINETICS AND THERMODYNAMICS STUDY

R. A. Mansour1*, S. M. Abobaker2andAdel M. Elmenshawy3

1-Chemical Engineering Department, High Institute of Engineering and technology, New

Damietta, Egypt

2-Chemical Engineering Department, High Institute of Engineering and technology, Borg

Alarab, Egypt

* Corresponding author, E-mail: [email protected]

ABSTRACT

Cellulose dialdehyde has been prepared and reacted with thiosemicarbazide to give

thiosemicarbazone modified cellulose (CTSC). A new and a relatively green methodology have

been developed for the selective separation of Ga(III) and In(III) ions. The batch removal of

Ga(III) and In(III) from aqueous solution under different experimental conditions using

economic adsorbents were investigated in this study. The effects of Ga(III) and In (III); initial

concentration, agitation time, adsorbent dosage, solution pH and temperature on CTSC

adsorption were investigated. Ga(III) and In(III) adsorption uptake were found to decrease with

increase in initial concentration, agitation time and increase with increase in temperature

solution whereas adsorption of Ga(III) and In(III) were more favourable at acidic pH 2.5 for

Ga(III) and (2-2.5) for In(III). The isotherm results were analyzed using the Langmuir,

Freundlich and Temkin isotherms. The pseudo-first order and pseudo-second order equations are

applied to model the kinetics of Ga(III) and In(III) ions adsorption onto CTSC kinetic model.

Thermodynamic parameters such as standard enthalpy (∆H), standard entropy (∆S), standard

free energy (∆G) were determined. A single stage batch adsorber was designed for adsorption of

Ga(III) and In(III)ions from aqueous solutions based on the optimum isotherm, and the treated

volume was calculated for different initial concentrations for Ga(III) and In(III).

Keywords; Modified cellulose, Ga(III) and In(III) adsorption, kinetics, isotherms,

thermodynamic parameters, Equilibrium model

1 INTRODUCTION

Heavy metals are elements having atomic weights between 63.5 and 200.6, and a specific

gravity greater than 5.0 (Srivastava &Majumder, 2008) With the rapid development of industries

such as metal plating facilities, mining operations, fertilizer industries, tanneries, batteries, paper

industries and pesticides, etc., heavy metals wastewaters are directly or indirectly discharged into

the environment increasingly, especially in developing countries. Unlike organic contaminants,

heavy metals are not biodegradable and tend to accumulate in living organisms and many heavy

metal ions are known to be toxic or carcinogenic. An increase in population initiating rapid

industrialization was found to consequently increase the effluents and domestic wastewater into

the aquatic ecosystem. Thus, the treatment of wastewater containing heavy metals has become a

major concern. Among the various metals, Ga(III) and In(III) are widely distributed in the earth's

crust and water system and present toxic manifestations when ingested by living systems (Bailar

et al, 1973) .These elements find several uses in industry. Gallium is used in electronic devices,

especially in the manufacture of gallium arsenide laser diodes, semiconductors and


178

superconductors. It has applications in aerospace, shipbuilding, cryogenics, medicine, atomic

reactors and electronic industry. Tooth decay, pain in joints and bones, nervous and

gastrointestinal disorders, heart pain and general disability are the effects of excessive exposure

or ingestion of Ga(III) or In(III), is a well-known poison and its action is cumulative. It causes

polyneuritis, convulsion, coma and even death (Bailar et al, 1973).Low concentrations of Ga(III)

and In(III) are not easily detected and high levels of potentially interfering constituents preclude

their direct determination. Various preconcentration tools are employed prior to their analysis

(Zhang et al, 2003). Liquid-liquid extraction (Rydberg et al,1992) is effective for separation and

preconcentration of cations, including these metals. Several researchers have studied the

fundamental extraction behavior and the mutual extractive separation of trivalent group 13 metal

cations using many kinds of extractants (Horiguchi et al, 2002; Liu et al 2006) . In spite of its

versatility, multi-stage extraction procedures, disposal of large volumes of organic wastes and

expensive treatment are the main problems. Solid phase extraction (SPE) has major advantages

over liquid-liquid extraction, including the fast, simple, direct application in micro level, no waste

generation, low risk of contamination, timeand cost-saving. Modified resins containing

methylene-diphosphonate (Alexandratos et al, 1996) ,carboxymethylphosphonate (Trochimczuk,

&Jezierska 1997), substituted malonamides (Trochimczuk 1998) and substituted

phenylphosphinic acid (Trochimczuk, 2000) have been applied for the separation of Ga(III) and

In(III). The use of many of the solvent extraction techniques has been limited because they are

expensive, often require long processes times, and cause the release of toxic materials. Cellulose,

which is a naturally occurring complex polysaccharide, is biodegradable and the most abundant

renewable organic raw material at low costs in the world. Modification of cellulose by graft

copolymerization and direct chemical modificationtechniques allows one to chemically change

the cellulose chain by introducing functional groups, which leads tonew cellulose products with

new properties (Mansour et al, 2015).

This paper reports on the use of modified cellulose to remove Ga(III) and In(III) from aqueous

solutions. The effect of metal ions concentrations, adsorbent dosage, pH, temperature, contact

time, adsorbent pretreatment is discussed.

2 MATERIALS AND TECHNIQUES

2.1. Buffered solution

Hydrochloric acid, sodium hydroxide and the other reagents were analytical grade (BDH

Chemicals Ltd. Poole, England). Solutions of pH 1- 8 were prepared by using hydrochloric acid

(0.1M) in double distilled water and adjusting the solutions to be required value with sodium

hydroxide (0.1M).

2.2. Preparation of the adsorbent

The cellulose derivate; dialdehyde cellulose (DAC) can be produced by employing periodate

as an oxidizing agent. During the periodate oxidation, selective cleavage of the C2-C3 bond of

the cellulose occurs, and two aldehyde groups are formed “Fig.1”. (David William O’Connell et

al, 2008). Cellulose is stirred in a 0.5% NaIO4 solution for 6h. The precipitate is washed with

bidistilled water with six times (30 ml for each time) and dried. Chemical immobilization with

thioseemicarbazide (CH5N3O) was performed as in our previous work (Mansour et al, 2015;

David William et al 2008).


179

Figure 1.Oxidation of cellulose by periodate followed by formation of thiosemicarbazone

2.3.Preparation of adsorbate

A stock solution of In(III) (1000 µg ml

–1) was prepared by dissolving 1g of In (Aldrich) in 5ml

concentrated nitric acid, the mixture was evaporated till dryness and then another 3ml were added

and the volume was completed to 1L with bidistilled water. Here a 1000µg ml–1

solution of

Ga(III) was prepared by dissolving 1g of Ga (Aldrich) in aqua regia (3ml HCl: 1ml HNO3) and

the mixture was diluted to 1L of bidistilled water. They were standardized by titration with

EDTA. Different volumes of this initial solution were put into 100 mL flask.

2.4.Instrumentation

The electronic spectra and the absorbance measurements of the Ga3+

ion with xylenol orange

(Makoto Otomo, 1965) at λmax = 573 nm and In3+

with 1-(2-pyridyl methylidene amine)-3-

(salicylideneamine) thiourea is proposed (Rosales et al, 1986) at λmax = 520 nm were recorded

using computer – controlled double beam UV–Vis spectrophotometer UV -2401 PC (Shimadzu,

Japan) with quartz cell (10 mm). The pH values were measured using a pH-meter (Hanna

Instruments, 8519, Italy) with accuracy of ±0.01 and standardized with variable mechanical

shaker (Corporation Precision Scientific, Chicago, USA) with constant speed of 240 rpm. A

simulated wastewater contaminated byGa(III) and In(III) were used for all experiments in this

study. Synthetic stock solutions were prepared by dissolving accurately weighed amounts of

Ga(III) and In(III) ions in one liter of double distilled water where desired concentrations were

obtained by successive dilution with distilled water.

2.5. Experimental technique

Adsorption studies were performed by the batch technique to obtain equilibrium data. The

batch technique was selected because of its simplicity. Batch experiment were carried out at

various pH (1-8), adsorbent dose (0.01 – 0.1g) and stirring speed (240 rbm) for a contact time of

20 min for Ga3+

and 30 min for In3+

. For each batch experiment, sample solution (100 ml)


180

containing 50 µg ml-1

of the studied metal ion was transferred to a 250 ml stopper glass bottle.

After setting pHand added desired amount of adsorbent(50mg) the mixture was agitated on

mechanical shaker for optimum time at 250C, after that the mixture was filtered to separate the

adsorbent from supernatant. The residual concentration of metal ions in supernatant was

determined by UV – vis spectrophotometer. All experiments were replicated thrice for all the

adsorbents and results were averaged. The removal percentage (R%) of the studied metal ions

were calculated for each run by the following expression:

% Removal = 𝑐𝑖 – 𝑐𝑓

𝑐𝑖 ∗ 100 (1)

Where Ci and Cf are the initial and final concentration of studying ions (Ga3+

and In3+

) in the

solution (mg/l).

2.6. Adsorption isotherms study

The adsorption capacity of an adsorbent which is obtained from the mass balance on the

sorbate in a system with solution volume V is often used to acquire the experimental adsorption

isotherms. Under the experimental conditions, the adsorption capacities of all the adsorbents for

each concentration ofGa(III) and In(III) at equilibrium were calculated using equation (2):

𝑞𝑒 =(𝑐𝑖– 𝑐𝑒)×𝑉

𝑚× 10

-3 (2)

where, qe represents the amount of metal uptake perunit mass of adsorbent (mg/g) at

equilibrium time, vis the volume of test solution (l), mis the mass of dryadsorbent (g), Ci and Ce

are the concentrations of metal ions in mg/l at initially and at equilibrium time, respectively. The

equilibrium studies that give the capacity of the adsorbent and adsorbate are described by

adsorption isotherms, which is usually the ratio between the quantity adsorbed and that remained

in solution at equilibrium at fixed temperature. Freundlich, Langmuir and Temkin isotherms are

the earliest and simplest known relationships describing the adsorption equation (Muhamad et al,

1998;Jalali et al, 2002). Adsorption isotherms are described in many mathematical forms, some of

which are based on a simplified physical picture of adsorption and desorption, while others are

purely empirical and intended to correlate the experimental data in simpleequations with two or

atmost, three empirical parameters: the more the number of empirical parameters, the better the fit

between experimental data (Motoyuki, 1990). Several isotherm models are available todescribe

this equilibrium sorption distribution.

2.6.1. Langmuir isotherm

The Langmuir equation is used to estimate the maximumadsorption capacity corresponding to

complete monolayer coverageon the adsorbent surface and is expressed by(Gesgel et al, 2003):

qe = (qmKLCe) /(1 + KLCe) (3)

The linearised form of the above equation after rearrangement is given by:

ce

qe =

1

qmce +

1

qm k l (4)

The experimental data is then fitted into the above equation for linearization by plotting Ce/qe

against Ce.


181

2.6.2. Freundlich isotherm

The Freundlich model named after Freundlich (1926) is an empirical equation used to estimate the

adsorption intensity of the sorbent towards the adsorbate and is given by (Kavith&Namasivayam, 2007)

n

eFe CKq /1)( (5)

The nature of isotherm is indicated by the slope 1/n. The adsorption is favorable if values of

slope 1/n lay between zero and one (Gecgel et al, 2003). The above equation is conveniently used

in linear form as:

lnqe = lnKF +(1/ n) ln Ce (6)

A plot of ln Ce against ln qe yielding a straight line indicates the conformation of the

Freundlich adsorption isotherm. The constants1/n and ln KF can be determined from the slope and

intercept, respectively.

2.6.3. The Temkin isotherm

The Temkin isotherm assume that the adsorption heat of all molecules in the layer decreases

linearly with coverage as a result of adsorbate/adsorbate interaction, and adsorption characterized

by a uniform distribution of binding energy (Kavith&Namasivayam, 2007) .The linear form of

Timken can be exposed as:

emtme CqKqq lnln (7)

Where: kt is Temkin constant which is related to adsorption capacity and maximum binding

energy (l/g), qe and Ce are the equilibrium concentration in solid phase (mg/g) and liquid phase

respectively (mg/l), qm is constant related to the heat of adsorption (J/mole)(Adouby et al, 2007).

2.7. Adsorption dynamics study

The study of adsorption dynamics describes the solute uptake rate and evidently this rate

controls the residence time ofadsorbate uptake at the solid–solution interface. Kinetics of Ga(III)

and In(III) adsorption on the modified cellulose were analyzed using pseudo first-order

(Lagergren, 1898), pseudo second-order (Ho et al., 2000). The conformity between experimental

data and the model predicted values was expressed by the correlation coefficients (r2, values close

or equal to 1). A relatively high r2 value indicates that the model successfully describes the

kinetics of Ga(III) and In(III) adsorption (Muhamad et al, 1998).

2.7.1. The pseudo first-order model

The pseudo first-order equation (Lagergren, 1898) is generally expressed as follows:

dqt= k1 (qe - qt) (8)

dt

After integration and applying boundary conditions t=0 to t=t and qt=0 to qt=qt, the integrated

form of Eq. (9) becomes:

log qe − qt = log qe − k1

2.303 t (9)


182

The values of log (qe−qt) were linearly correlated with t. The plot of log (qe−qt) vs. t should

give a linear relationship from which k1and qe can be determined from the slope and intercept of

the plot, respectively.

2.7.2. The pseudo second-order model

Ho and McKay pseudo second order kinetic model can be expressed as:

𝑡

𝑞𝑡 =

1

𝑘2 𝑞𝑒2 +

1

𝑞𝑒 t (10)

Where: k2is the second order rate constant (g/mg min) (Hameed et al., 2009; Eren et al.,

2010).

2.8. Thermodynamic studies

The aim of thermodynamic study is to determine thermodynamic parameters such as free

energy (ΔG), enthalpy (ΔH), and entropy (ΔS). Thermodynamic parameters used to determine the

spontaneity of the adsorption (Suteu&Zaharia, 2011)

ΔG = -RTlnk (11)

K = qe/Ce (12)

ΔG = ΔH - T ΔS (13)

The sorption enthalpy (ΔH, Jmol-1

) was specified by the slopes (ΔH/R), and the entropy (ΔS,

Jmol-1

k-1

) was specified by the intercepts (ΔS/R). Finally, free Gibbs energy was calculated

using the above equation number (13) (Recep&Birnur, 2013).

3. RESULTS AND DISCUSSION

3.1. Effect of Ph

The pH of solution has a significant impact on the uptake of heavy metals, since it determines

the surface charge of the adsorbent, the degree of ionization and speciation of adsorbate (Panday

et al, 1985;Nomanbhay et al, 2005). It is known that sorption of heavy metal ions by solid

substrates depends on the pH of the solution. “Fig.2” shows that uptake capacity and % removal

of Ga(III) and In(III) by modified cellulose decreased with increased in pH. It is generally known

that at low pH values, solution is strongly acidic and the surface of the sorbent is surrounded by

hydrogen ions, which prevent the metal ions from approaching the binding sites on the sorbent.In

order to establish the effect of pH on the sorption of Ga3+

and In3+

ions, the batch equilibrium

studies at different pH values was carried out in the range of 1-8.The experiment was elaborated

by shaking the solution containing the metal ion with the CTSC of variable acidity for sufficient

equilibrium time. Figure 2 shows the maximum sorption efficiency of CTSC for Ga(III) at pH

2.5 and for In(III) at 2- 2.5. At higher pH sorption capacity and % removal decreased and this

can be explained by the fact that at higher pH, the number of hydroxyl ions is more and chances

of formation of metal hydroxides are also more that result in precipitation. This precipitation

caused a decrease in sorption capacity and % removal with increase in pH.


183

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0

10

20

30

40

50

60

70

80

90

100

110

Reco

very,

%

pH

In(III)

Ga(III)

Figure 2. Effect of pH on the adsorption of Ga(III) and In (III) using CTSC.

3.2. Effect of contact time

Effect of contact time on the rate of adsorption using CTSC was achieved as shown in “Fig.3”. The

experiments were performed at natural pH, 250 C temperature and adsorbent dose of 0.05gm /100mL

solution.The rate of percent removal for Ga3+

reached to 100% after 20 min and In3+

after 30 min. This is

probably due to larger surface area of the leaves being available at beginning for the adsorption of Ga3+

and In3+

ions. The rate of adsorption decreased with time due to decrease in the concentration gradient

(driving force) which indicates that the adsorbent is saturated at this level and the adsorption reaches its

maximum value (Hameed et al, 2009).

Figure 3. The effect of time on the removal of Ga(III) and In(III) usingCTSC

3.3. Effect of temperature

Thermodynamic parameters are dependent on temperature which indicates if the adsorption is

exothermic or endothermic(Barakat et al, 2009). In this study, the effect of temperature on the

separation efficiency of Ga3+

and In3+

ions was studied by applying the optimal conditions with

different temperatures (26 - 550C). The data present in “Fig.4” indicate that, there is an increase

in the removal percentage of the studying metal ions with increasing temperature that indicate the

adsorption is endothermic for both Ga(III) and In(III) ions onto CTSC.

0

20

40

60

80

100

120

0 10 20 30 40 50

% R

eco

very

Time, min.

In(III)

Ga(III)


184

Figure 4. Effect of temperature on the adsorption of studying metal ions

3.4. Adsorption kinetics

Adsorption kinetics provides the details on the adsorption mechanism of adsorbate onto an

adsorbent. The kinetics of heavy metals (Ga3+

and In3+

) adsorption onCTSC was examined with

thepseudo first-order and pseudo-second order.The kinetic models tested for an initial

concentration of 50ppm of studying heavy metals are shown in table 1. It was clearly that the

kinetics of Ga+3

and In+3

removed by CTSC followed the pseudo secondkinetic model “Fig.5”

with correlation coefficient R2 is 0.987 for Galium III and 0.975 for Indium III yields very good

straight lines.

Table 1. Calculated kinetic parameters for pseudo first order and pseudo second order kinetic

models for the adsorption of Ga3+

and In3+

using CTSC as adsorbent

0102030405060708090

0 10 20 30 40 50 60%

Re

cove

ryTemperature, 0C

In(III)

Ga(III)

R2 Isotherm parameters Adsorption

Kinetics

NO

In(III) Ga(III) In(III) Ga (III)

0.88 0.94 k1=2.076

qe= 0.0494

k1= 2.001

qe=-0.0483

Pseudo

First-Order

1

0.975 0.987 k2= 0.1617

qe=0.011

k2= 0.0574

qe= 0.0146

Pseudo

Second-

Order

2


185

Figure 5. Pseudo second order kinetics for Ga(III) and In(III) onto CTSC

3.5. Adsorption isotherms

The purpose of the adsorption isotherms is to relate the adsorbate concentration in the bulk

and the adsorbed amount at the interfaceand is important for the design of adsorption system. The

isotherm results were analyzed using the Langmuir, Freundlich and Temkin isotherms models

(shown in Table 2)find common use for describing adsorption isotherms for water and

wastewater treatment application (Gecgel et al, 2013). Table 3 shows the values of constants and

correlation coefficients of the three isotherms. The correlation coefficient from the three

equations indicates that Langmuir model yields a better fit for experimental data than the other

model, for both Ga(III) and In(III). This means that the adsorption is monolayer and takes place

on homogeneous surfaces.

Table 2. Isotherm models and their linearized expression with their parameters.

Isotherm Equation Linear expression Plot Parameters

Langmuir )1()( eLeLme CKCKqq

Type I:

meLmee qCKqqC /)/(1/

eee CvsqC . / mL qK &

Type II:

meLme qCKqq /1)/(1/1

ee Cvsq 1/ . /1 mL qK &

Type III: )/( eLeme CKqqq ee Cvsq /q . e mL qK & Type IV: eLmLee qKqKCq / ee qvsq ln . /Ce

mL qK &

Freundlich n

eFe CKq /1)( eFe CnKq ln)/1(lnln ee Cvsq ln . ln

nKF &

Temkin )ln( eTme CKqq emTme CqKqq lnln ee Cvsq ln . mT qK &

y = 0.011x + 0.160R² = 0.975

y = 0.014x - 0.057R² = 0.987

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0 10 20 30 40 50

t/q

t

Time, min.

In(III)

Ga(III)


186

Table 3. Isotherm parameters for adsorption of Ga(III) and In(III) ions from aqueous solutions onto

CTSC.

R2 Isotherm Parameters

Adsorption

Isotherm

NO

In(III) Ga(III) In(III) Ga(III)

0.9963 0.9997 qm = 89.28 qm = 92.59 Langmuir 1

KL = 0.048 KL = 0.7886

0.841 0.8161 Kf = 16.6 Kf = 84.7 Freundlich 2

n = 3.06 n = 73.5

0.859 0.7118 qm = 0.0279 qm = 1.048 Tempkin 3

Kt = 3.8x1024

Kt =2.78x1035

Figure 6. Langmuir model for adsorption of Ga(III) onto CTSC

Figure 7. Langmuir model for adsorption of In(III) onto CTSC

Figure 8. Freundlich model for of Ga(III) onto CTSC


187

Figure 9. Freundlich model for adsorption of In(III) onto CTSC

Figure 10. Temkin model for adsorption of Ga(III) onto CTSC

Figure 11. Temkin model for adsorption of In(III) onto CTSC

y = 0.326x + 2.810R² = 0.841

0

1

2

3

4

5

0 1 2 3 4 5 6

Ln q

e

Ln Ce

y = 0.027x + 1.580R² = 0.859

00.5

11.5

22.5

33.5

44.5

5

0 20 40 60 80 100

qe

ln Ce


188

3.6. Adsorption Thermodynamics

1/T as a function of lnqe/Ce is depicted in “Fig.12“and shows the temperature dependence of

the adsorption of the studied ions. The thermodynamic parameters ΔH,ΔG and ΔS were

calculated employing the equations and introduced in Table 4, the value of enthalpy presented in

the table are for the Ga(III) and In(III) ions (Ga3+

: 17.3 KJmol-1

; In3+

6.648 KJmol-1

). The

enthalpy change for the adsorption was ΔH > 0 for Ga(III) and In(III) ions for CTSC; that is to

say, the overall process are endothermic. ΔG for Ga(III) -2.799 KJmol-1

and for In(III) -1.49

KJmol-1

.

The negative value of ΔG indicates the spontaneous nature of the adsorption of Ga(III) and In(III)

onto CTSC. The entropy change was positive ΔS > 0 for Ga(III) and In(III) ions (Ga3+

: 64.9

mol-1

K-1

; In3+

26.39 mol-1

K-1

).

Figure 12. Graphical determination of thermodynamic parameters

3.7. Process design

Adsorption process proceeds through varies mechanism such as external masstransfer of solute

onto adsorbent followed by intraparticle diffusion. Unless extensive experimental data are

available concerning the specific sorption application design procedures based on sorption

equilibrium conditions are the most common methods to predict the adsorber size and

performance. The design of batch adsorber depend on equilibrium data obtained from

experimental work (Mahmoudi et al., 2014) are the most common method to predict the amount

of adsorbent needed and the size of adsorber.

A schematic diagram of a batch sorption process is shown in “Fig13”. The design objective is to

reduce the Ga(III) liquid volume V(l) from an initial concentration of C0 to C1 (mg/l). The amount

of adsorbent (CTSC) is M and the solute loading changes from q0 to q1 (mg/g). At time t=0, q0=0

and as time proceeds the mass balance equates Ga(III) removed from the liquid to that picked up

by the solid.

y = -2092.x + 7.877

y = -799.1x + 3.173

0

0.2

0.4

0.6

0.8

1

1.2

1.4

1.6

0.003 0.0031 0.0032 0.0033 0.0034

Ln q

e/C

e

1/T

Ga(III)

In(III)


189

Figure 13. A single-stage batch adsorber for removal of Ga(III) from aqueous solutions

The mass balance for the Ga3+

in the single-stage is given by:

10110 )()( MqqqMCCV (14 )

At equilibrium conditions, C1→Ce and q1→qe

For the adsorption of Ga3+

on CTSC, the Langmuir isotherm gives the best fit to experimental

data. Consequently equation can be best substituted for q1 in the rearranged form of Eq. (15)

giving adsorbent/solution ratios for this particular system,

)1/()(

00

1

10

kLCeqmkLCe

CC

q

CC

q

CC

V

M e

e

e

(15)

“Fig.14” shows a series of plots (60, 70, 80 and 90% Ga3+

removal at different solution

volumes, i.e., 1, 2, 3, 4, 5, 6, 7 and 8 L) derived from Eq. (16) for the adsorption of Ga3+

on CTSC

at initial concentration of 50 mg/L. The amount of CTSC required for the 90% removal of Ga3+

solution of concentration 50 mg/L was 1.43, 2.867, 4.29 and 5.72 g for Ga3+

solution volumes of

1, 2, 3 and 4 L, respectively.

Figure 14. Volume of effluent treated versus mass of CTSC for different percentage removal of 100

mg/l Ga(III) ion concentration.

V

C0

V

C1

M

q0

M

qe

0

2

4

6

8

10

12

0 1 2 3 4 5 6 7 8 9

Tre

ate

d v

olu

me

(lit

er)

Mass of adsorbent (g)

60%R

70%R

80%R

90%R


190

4. CONCLUSION

The present study shows that, a novel adsorbent (CTSC), was synthesized, and its

adsorpative features were investigated for Ga(III) and In(III) ions. The removal of Ga3+

and In3+

from aqueous solution is a rapid process, at pH 2.5 for Ga(III) and pH 2-2.5 for

In(III). The equilibrium data of both heavy metals (Ga3+

and In3+

) fits well with Langmuir

isotherm. The kinetic data are very well with the pseudo second order for Ga3+

and In3+

.

The positive value of ΔH indicates that the process is endothermic for both Ga(III) and In

(III) ions.The percent removal of heavy metals onto CTSC reached to 100% after 20 min

for Ga(III) and 30 min In(III) at 50ppm. Thus, Application of this study may be highly useful

in designing the cost effective and highly efficient technique for heavy metals effluent

techniques.

ABBREVIATIONS Ce Equilibrium metal ion concentration (mg/L)

Ci Initial metal ion concentration (mg/L)

Cf Final metal concentration, mg/L

CTSC Cellulose thiosemicarbazone D Constant related to the energy of adsorption (L/mg)

DAC Dialdehydecellulose

DP Date Pits

Kf Adsorption capacity

M Mass of adsorbent (g)

M Molarity

nAdsorption intensity by Freundlich isotherm model

qe Equilibrium adsorption capacity (mg/g)

qm Empirical Constant by Langmuir isotherm model, mg/g

R Universal gas constant (8.314 J/mol/K)

T Temperature in Kelvin (K)

V Volume of the solution (L)

ACKNOWLEDGEMENT

This work is supported by the high institute for engineering and technology in new Damietta-

Egypt, which the author is grateful.

REFEERENCES

Adouby, K., KoffiAkissi, L.C., Eboua,Wandan, N., Yao, B.,( 2007). Removal of

heavy metal ions (Pb2+

, Cu2+

) in aqueous solutions by Ptrygotamacrocarpa sawdust. J.

Applied Sci. 7(14), 1864-1872.

Alexandratos, S. D., Trochimczuk, A.W., Horwitz, E.P., and. Gatrone, R.C., (1996).

Synthesis and characterization of a bifunctional ion exchange resin with polystyrene-

immobilized diphosphonic acid ligands. J. Appl. Polym. Sci., 61, 273.

Bailar, J.C., Emeleus, H.J., Nytholm, R. and Trotman-Dickenson, A.P. (1973)

“Comprehensive Inorganic Chemistry”,1st ed., Pergamon, London.


191

Barakat, M., Nibou, D., Chegrouche, S., Mellah, A.,(2009). Kinetics and

thermodynamics studies of Cr(VI) ions adsorption onto activated carbon from aqueous

solutions.Chemical Engineering and processing, 48 (1), 38-47.

David William O’Connell, Colin Birkinshaw, Thomas Francis O’Dwyer,

(2008).Heavy metal adsorbents prepared from the modification of cellulose: A review,

Bioresource Technology, 99, (15), 6709–6724.

Eren, E., Cubuk, O., Ciftci, H.,Eren, B., Caglar, B., (2010). Adsorption of basic dye

from aqueous solutions by modified sepiolite: Equilibrium, kinetics and thermodynamics

study. Desalination. 252(1-3), 88-69.

Geçgel, Ü.,Özcan, G., Gürpınar, G.Ç., (2013). Removal of methylene blue from aqueous

solution by activated carbon prepared from Pea Shells (Pisumsativum). J. Chem., 1-9.

Hameed, B.H., Salman, J.M., Ahmed, A.L., (2009). Adsorption isotherm and kinetic

modeling of 2,4-D pesticide on activated carbon derived from date stones.J.Hazard, 163

(1), 121-126.

Horiguchi, R., Nukatsuka, I, Shimizu, Y, Sekikawa, S and Ohzeki, K,(2002).

Removal and recovery of lead using nonliving biomass of marine algaeBunseki Kagaku,

51, 675.

Jalali, R. Ghafourian, H., Asef, D. Sepehr, S. (2002). Removal and recovery of lead

using nonliving biomass of marine algae. J. Hazard Matter 92, 253–262. Kavitha, D., Namasivayam, C.,(2007). Experimental and kinetic studies on methylene

blue adsorption by coir pith carbon. Bioresource Technology. 98, 14–21.

Lagergren s., Sven, B.K., (1898) Ventenskapasakad. Handl, 24.

Liu, J.S., Chen, H, Chen, X. Y., Guo, Z. L., Hu, Y. C., Liu, C. P., and Sun, Y.Z.

(2006). Extraction and separation of In(III), Ga(III) and Zn(II) from sulfate solution using

extraction resin. Hydrometallurgy, 82, 137.

Mansour, R.A., El-Menshawy A.M., and Eldesoky, A.M., (2015). Separation of Uranyl

Ion from Different Media Using a New Cellulose Hydrazone: Adsorption Isotherms, Kinetic

and Thermodynamic Studies, International Journal of Advanced Research. 3, 966-980

Mahmoudi, K., Hamdi, N., Srasra, E., (2014). Preparation and characterization of activated

carbon from date pits by chemical activation with zinc chloride for methyl orange adsorption. J.

Mater. Environ. Sci., 5 (6), 1758-1769.

Makoto Otomo, (1965). The Spectrophotometric Determination of Gallium(III) with

XylenolOrange. Bulletin of Chemical Society of Japan, 38 (4), 624-629

Motoyuki, S., (1990).Adsorption Engineering, Elsevier Sci. Publishers, pp. 5–61.

http://www.sciencedirect.com/science/article/pii/S0960852408000710



http://www.sciencedirect.com/science/journal/09608524

http://www.sciencedirect.com/science/journal/09608524/99/15


192

Muhamad, N.,Parr,J., Smith, D. M.,Wheathey, D.A., (1998) WEDC conference

sanitation and water for all, Islamabad, Pakistan, pp. 346–349.

Nomanbhay, S. M.; palanisamy, k., (2005). Removal of heavy metal from industrial

wastewater usingchitosan coated oil palm shell charcoal. Electronic J. Biotechnol. 8, 43-53

Panday,k.k.; prased G.; Singh, N.V., (1985). Copper(II) removal from aqueous

solutions by fly ash water Res. ,19, 869-873

RecepAkkaya, birnurAkkaya, (2013). Adsorption isotherms, kinetics,

thermodynamics and desorption studies for uranium and thorium ions from aqueous

solution by novel microporous composite P(HEMA-EP), Journal of nuclear materials,

434,328-333.

Rosales D1, Millan I, Gomez Ariza JL, (1986). Spectrophotometric determination of

indium in nickel alloys and zinc ores with 1-(2-pyridylmethylideneamine)-3-

(salicylideneamine)thiourea,Talanta. 33, 607-610.

Rydberg, J. Musikas, C. and Choppin,G.R.(1992) “Principles and Practices of

Solvent Extraction”, Marcel Dekker, New York.

Srivastava, N.K., Majumder, C.B.,( 2008). Novel biofiltration methods for the treatment

of heavy metals from industrial wastewater. J. Hazard. Mater. 151, 1-8.

Suteu, D., Zaharia, C.,( 2011). Sawdust as biosorbent for removal of dyes from

wastewaters. Kinetic and thermodynamic study. Chem. Bull. "POLITEHNICA" Univ.

(Timisoara). 56(70), 85-88.

Trochimczuk, A. W., andJezierska, J, (1997). Selective hydrolysis of polymer-bound

ethoxycarbonylethylphosphonate and e.p.r. studies of Cu(II) complexes with the parent

resin and its derivatives,Polymer, 38, 2431.

Trochimczuk, A.W., (1998). Chelating resins with N-substituted diamides of malonic

acid as ligands Eur. Polym. J., 34, 1657.

Trochimczuk, A.W. (2000) Synthesis of functionalized phenylphosphinic acid resins

through Michael reaction and their ion-exchange properties.React. Funct. Polym. 44, 9.

removal of heavy metals from aqueous ...iwtc.info/wp-content/uploads/2017/05/31.pdf2017/05/31 ·...

Documents